EP0657026B1 - Verfahren zur isotopenanalyse mittels der optischen emissionsspektometrie eines durch laserenergie erzeugten plasma - Google Patents

Verfahren zur isotopenanalyse mittels der optischen emissionsspektometrie eines durch laserenergie erzeugten plasma Download PDF

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Publication number
EP0657026B1
EP0657026B1 EP94918923A EP94918923A EP0657026B1 EP 0657026 B1 EP0657026 B1 EP 0657026B1 EP 94918923 A EP94918923 A EP 94918923A EP 94918923 A EP94918923 A EP 94918923A EP 0657026 B1 EP0657026 B1 EP 0657026B1
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EP
European Patent Office
Prior art keywords
analysis
sample
plasma
laser
isotopic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94918923A
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English (en)
French (fr)
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EP0657026A1 (de
Inventor
Patrick Mauchien
Walter Pietsch
Alain Petit
Alain Briand
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orano Cycle SA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Compagnie Generale des Matieres Nucleaires SA
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited

Definitions

  • the subject of the present invention is a method isotopic analysis by emission spectrometry optics on plasma produced by laser.
  • the isotopic concentration measurements of elements are usually performed by spectrometry massive.
  • the sample to be analyzed is dissolved then atomized and thermally ionized.
  • the ions are then separated according to their mass before being accounts.
  • Mass spectrometry is characterized by a very good sensitivity and excellent accuracy of measures. However, in addition to the fact that it requires preparative chemistry for the dissolution of samples, this is a technique that implements sophisticated and expensive devices, which cannot be used only in laboratory.
  • Another technique for measuring isotopic concentrations involves analyzing spectrally the emission radiation from a source of excited atoms. In this case, we separate, using a spectrometer, emission wavelengths, these can be very slightly different for several isotopes of the same element (effect of isotopic displacement). Measuring concentrations isotopic is then obtained by measuring the signal corresponding to each isotope.
  • Optical emission spectrometry on plasma induced by high frequency puts implement this principle and has, for example, been used for isotopic analysis of uranium. This technique is fast and relatively economical. However, it is not very precise and, like the spectrometry of mass, it cannot be considered for a use outside the laboratory.
  • Alpha count spectrometry can also be considered for radioactive elements. It's a inexpensive technique, relatively simple to implement artwork. It can also be used to direct analysis of solid samples. Its field application is however very limited. The alpha particles detected are those emitted by the surface atomic layers, the others being absorbed into the sample. This means that the measurement is only representative of the area of the sample. Mass analysis therefore requires a preparative chemistry (dissolution of the sample and preparation of very thin deposits).
  • Another limiting factor is linked to the concentration of radioactive material.
  • concentration a few mg / cm 2
  • interference is observed (overlapping of the corresponding peaks U 234 , U 235 , U 238 ).
  • the counting times are very long (several minutes, even several tens of minutes).
  • the level of precision of alpha spectrometry for isotopic analysis is at the level of a few percent.
  • Gamma counting spectrometry presents promising performances for isotopic analysis of uranium. It is an analytical technique not destructive which also offers the possibility of direct determination of the mass of uranium. By however, the counting (and therefore analysis) times are very long. It only addresses elements radioactive and it doesn't allow mapping the isotopic composition of the samples. Finally, it cannot be considered as a technique "in situ" analysis.
  • This process is used for example for copper, stainless steel, molybdenum, tungsten and graphite. It is convenient to determine the elementary composition of the sample, but it does not, a priori, make it possible to perform an isotopic analysis, which requires a much finer analysis. Indeed, the isotopic displacements are in general much weaker than the spectral displacements corresponding to different elements.
  • the object of the present invention is precisely to SEO / PPL type process but whose conditions are such as isotopic analysis becomes possible.
  • the first condition to be fulfilled is that each pulse of the laser beam has an energy less than or equal to 10 mJ / cm 2 .
  • a second condition must be satisfied: the spectral analysis must be carried out with some delay from the laser pulse. This delay is at least 200 ns.
  • the analysis of the light emitted by the plasma must relate to a volume of plasma located some distance from the surface of the sample, equal to at least 0.5 mm.
  • the invention can be applied to elements which exhibit significant isotopic displacement, including uranium and plutonium, but also to Rare earths (Nd, Sm, Gd, Er,) or even tungsten.
  • FIG. 1 The schematic diagram of an apparatus putting in the invention is given in figure 1.
  • the sample to analyze 10 is placed in an enclosure 12 in which the pressure is maintained at a few tens of mtorr using conventional means 14 (pump 15, filter 16, pressure measuring device 17, etc.).
  • a laser beam 20 is directed on the sample. he is produced by a laser source 22.
  • This laser can be of the XeCl or Nd: YAG type or of any other type. he preferably works on impulse.
  • the energy deposited on the sample 10 by the laser beam 20 causes the material to be torn off and the formation of a light plasma 13.
  • Part of the light emitted by a precise volume fraction of the plasma 13, is collected and focused on the entry slit 28 of a spectrometer 30 at high spectral resolution, and this by a simple optical system 32 using the combination of several lenses or / and one or more optical fibers not shown.
  • the spectrometer 30 makes it possible to separate the different radiations coming from the plasma.
  • the light signal is collected on one or more photomultipliers, or on a multichannel detector.
  • An amplification, signal processing and control chain 34 is associated with the spectrometer 30 and the laser 22.
  • certain experimental conditions must be respected to obtain emission line widths compatible with an isotopic analysis. It is necessary to control a certain number of experimental parameters like the laser energy of irradiation of the samples and the spatio-temporal conditions of measurement.
  • the laser energy must not exceed a few milliJoules per cm 2 and per pulse (for example less than 10 mJ / cm 2 ); beyond that, the plasma is too dense and too hot and the emission lines widen considerably.
  • the emission signal must be collected in a volume located at a distance from the surface of the sample, at least 0.5 mm from it.
  • the time delay between the laser pulse and the instant of the measurement must be at least 200 ns.
  • FIG. 2 shows an example of the result obtained with a sample of enriched metallic uranium (93.5% U 235 , 5.3% U 238 and 1.2% U 234 ).
  • the plasma was produced by an XeCl laser focused on a micro-region.
  • the spectrum represents the recording of the plasma emission signal over a spectral range of 0.085 nm around the atomic transition at 424.4372 nm of the uranium ion.
  • the intense peak (width at half height equal to 0.01 nm) is due to the emission of the isotope U 235 .
  • a second less intense peak corresponding to the emission of U 238 .
  • the spectral displacement between the two peaks is 0.025 nm, which corresponds to the known isotopic displacement for this line.
  • the intensity ratio U 235 / U 238 is equal to 16.7 while the true concentration ratio is 17.64 (93.5% / 5.3%). This 16.7 ratio leads to an error of 5% on the determination of the U 238 concentration (5.6% instead of 5.3%) and 0.3% on the determination of U 235 (93.2 % instead of 93.5%).

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Claims (5)

  1. Verfahren zur Analyse einer Probe, darin bestehend:
    die zu analysierende Probe (10) mit einem Pulslaserstrahl (20) zu bestrahlen, um an seiner Oberfläche ein Plasma (13) zu erzeugen,
    das Spektrum (30) des durch dieses Plasma (13) abgestrahlten Lichts zu analysieren,
    daraus die Zusammensetzung der Probe (10) abzuleiten,
    dadurch gekennzeichnet,
    daß die Analyse eine Isotopenanalyse ist, und dadurch, daß jeder Impuls des Laserstrahls (20) eine Energie kleiner oder gleich 10mJ/cm2 hat.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Analyse des Spektrums mit einer bestimmten Verzögerung in bezug auf den Laserstrahl erfolgt.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Verzögerung wenigstens gleich 200ns beträgt.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Analyse des durch das Plasma abgestrahlten Lichts ein Plasmavolumen betrifft, das zu der Oberfläche der Probe einen Abstand von wenigstens 0,5mm aufweist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Probe aus Uran oder aus Plutonium ist.
EP94918923A 1993-06-15 1994-06-14 Verfahren zur isotopenanalyse mittels der optischen emissionsspektometrie eines durch laserenergie erzeugten plasma Expired - Lifetime EP0657026B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9307179 1993-06-15
FR9307179A FR2706614B1 (fr) 1993-06-15 1993-06-15 Procédé d'analyse isotopique par spectrométrie d'émission optique sur plasma produit par laser.
PCT/FR1994/000708 WO1994029699A1 (fr) 1993-06-15 1994-06-14 Procede d'analyse isotopique par spectrometrie d'emission optique sur plasma produit par laser

Publications (2)

Publication Number Publication Date
EP0657026A1 EP0657026A1 (de) 1995-06-14
EP0657026B1 true EP0657026B1 (de) 1998-12-16

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EP94918923A Expired - Lifetime EP0657026B1 (de) 1993-06-15 1994-06-14 Verfahren zur isotopenanalyse mittels der optischen emissionsspektometrie eines durch laserenergie erzeugten plasma

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US (1) US5627641A (de)
EP (1) EP0657026B1 (de)
JP (1) JPH08503779A (de)
KR (1) KR100326286B1 (de)
CA (1) CA2142351A1 (de)
DE (1) DE69415287T2 (de)
ES (1) ES2127400T3 (de)
FR (1) FR2706614B1 (de)
WO (1) WO1994029699A1 (de)

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DE19531988A1 (de) 1995-08-30 1997-03-06 Europaeische Kommission Fernmessung von U (Pu) in Gläsern
SE512313E (sv) 1998-06-03 2004-03-16 Valinge Aluminium Ab Låssystem samt golvskiva
US6400787B2 (en) * 1998-07-06 2002-06-04 Euratom Telemetering of uranium of plutonium in glass
GB2359886A (en) * 2000-03-04 2001-09-05 Applied Photonics Ltd Laser spectroscopic remote detection of surface contamination
KR100433684B1 (ko) * 2001-11-21 2004-06-02 한국수력원자력 주식회사 레이저 동위원소 분리과정에서 생성물의 질량성분신호를이용한 파장가변 레이저 파장의 실시간 궤환제어 방법
US7113277B2 (en) * 2003-05-14 2006-09-26 Lockheed Martin Corporation System and method of aerosolized agent capture and detection
US10222337B1 (en) 2008-05-05 2019-03-05 Applied Spectra, Inc. Laser ablation analysis techniques
US9997325B2 (en) * 2008-07-17 2018-06-12 Verity Instruments, Inc. Electron beam exciter for use in chemical analysis in processing systems
CN103822810A (zh) * 2014-02-24 2014-05-28 攀钢集团成都钢钒有限公司 一种光电直读光谱分析仪用试样的制备方法
CN104297170A (zh) * 2014-10-22 2015-01-21 合肥卓越分析仪器有限责任公司 一种光电直读光谱分析仪的废气处理装置

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GB1024687A (en) * 1965-02-13 1966-03-30 Ford Motor Co Laser excitation of atomic spectra
US4794230A (en) * 1984-02-16 1988-12-27 The United States Of America As Represented By The United States Department Of Energy Low-pressure water-cooled inductively coupled plasma torch
JPH06100544B2 (ja) * 1986-07-10 1994-12-12 川崎製鉄株式会社 レーザ発光分光分析装置
US5133901A (en) * 1991-03-01 1992-07-28 Westinghouse Electric Corp. System and method for on-line monitoring and control of heavy metal contamination in soil washing process

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Publication number Publication date
FR2706614A1 (fr) 1994-12-23
FR2706614B1 (fr) 1995-07-13
WO1994029699A1 (fr) 1994-12-22
US5627641A (en) 1997-05-06
DE69415287T2 (de) 1999-06-24
KR950703143A (ko) 1995-08-23
CA2142351A1 (en) 1994-12-22
EP0657026A1 (de) 1995-06-14
ES2127400T3 (es) 1999-04-16
KR100326286B1 (ko) 2002-11-07
JPH08503779A (ja) 1996-04-23
DE69415287D1 (de) 1999-01-28

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